Supported catalyst for olefin polymerization

ABSTRACT

Disclosed are catalyst systems and methods of making the catalyst systems for the polymerization of an olefin containing a solid titanium catalyst component containing an inorganic titanium compound, a magnesium alcohol adduct made from an inorganic magnesium compound and an alcohol, and a porous support having at least one of a certain specific surface area, a certain pore volume, and a certain median particle size. The catalyst system may further contain an organoaluminum compound and optionally an organosilicon compound. Also disclosed are methods of making polyolefins.

FIELD OF THE INVENTION

The subject invention generally relates to supported olefinpolymerization catalyst systems catalyst systems for making olefinpolymers and methods of making the catalyst systems and olefin polymers.

BACKGROUND

Polyolefins are a class of polymers derived from simple olefins. Knownmethods of making polyolefins involve the use of Ziegler-Nattapolymerization catalysts. These catalysts polymerize vinyl monomersusing a transition metal compound to provide a stereoregulated polymer.

Numerous Ziegler-Natta polymerization catalysts exist. The catalystshave different characteristics and/or lead to the production ofpolyolefins having diverse properties. Moreover, polyolefins made withthe use of Ziegler-Natta polymerization catalysts vary instereoregularity, molecular weight distribution, impact strength,melt-flowability, rigidity, heat sealability, isotacticity, and thelike.

Silica supported Ziegler-Natta polymerization catalysts generally aremade through a precipitation method using an organic magnesium compoundstarting material. The organic magnesium compound is chlorinated toprovide magnesium chloride. However, the chlorination procedure tends tobadly corrode manufacturing equipment and introduces harmfulenvironmental concerns.

SUMMARY

The following presents a simplified summary of the invention in order toprovide a basic understanding of some aspects of the invention. Thissummary is not an extensive overview of the invention. It is intended toneither identify key or critical elements of the invention nor delineatethe scope of the invention. Rather, the sole purpose of this summary isto present some concepts of the invention in a simplified form as aprelude to the more detailed description that is presented hereinafter.

The subject invention provides olefin polymerization catalyst systems,methods of making the olefin polymerization catalyst systems, andmethods of polymerizing (and copolymerizing) olefins involving the useof a solid titanium catalyst component containing a porous supporthaving certain physical characteristics. Use of the porous support, andinorganic magnesium and titanium compounds provides an olefinpolymerization catalyst system with at least one of high catalystefficiency, low cost, environmentally friendly manufacturing techniques,the production of polymer particles having desired (controllable)morphology, the production of polymer particles having desired bulkdensity, and the production of impact copolymer with a high ethylenecontent.

To the accomplishment of the foregoing and related ends, the inventioncomprises the features hereinafter fully described and particularlypointed out in the claims. The following description and the annexeddrawings set forth in detail certain illustrative aspects andimplementations of the invention. These are indicative, however, of buta few of the various ways in which the principles of the invention maybe employed. Other objects, advantages and novel features of theinvention will become apparent from the following detailed descriptionof the invention when considered in conjunction with the drawings.

BRIEF SUMMARY OF THE DRAWINGS

FIG. 1 is a high level schematic diagram of an olefin polymerizationsystem in accordance with one aspect of the subject invention.

FIG. 2 is a schematic diagram of an olefin polymerization reactor inaccordance with one aspect of the subject invention.

FIG. 3 is a high level schematic diagram of a system for making impactcopolymer in accordance with one aspect of the subject invention.

DETAILED DESCRIPTION

The subject invention relates to solid titanium catalyst components,catalyst systems, methods of making solid titanium catalyst componentsand catalyst systems, and methods of making polyolefins includingpolyethylenes such as high density polyethylene (HDPE) and linear lowdensity polyethylene (LLDPE), polypropylene, ethylene-propylenecopolymers, and impact copolymers, such as polymer rubber intimatelymixed in a polyolefin matrix.

An aspect of the invention involves forming the catalyst support from aninorganic magnesium compound, an alcohol, and solid, porous supporthaving certain physical characteristics. Use of the inorganic magnesiumcompound, an alcohol, a solid, porous support having certain physicalcharacteristics eliminates the need to chlorinate an organometallicmagnesium compound, and since a chlorination procedure is eliminated,undesirable environmental concerns are mitigated (harmful waste streamsare mitigated). Corrosion of manufacturing equipment caused bychlorination procedures is also eliminated. Moreover, use of aninorganic magnesium compound is much less expensive than using anorganometallic magnesium compound, thereby reducing costs of catalystmanufacture.

There are a number of benefits associated with the solid titaniumcatalyst components. The use of the porous support having certainphysical characteristics and inorganic magnesium compound alsocontributes to the ability to form a solid titanium catalyst componentof substantially spherical shape. The substantially spherical shape ofthe solid titanium catalyst component contributes to the ability of thecatalyst system in various polymerization methods to provide an improvedlevel of control over the properties of the resultant polymer products(properties such as bulk density, glass transition temperature, adhesionproperties, coefficients of temperature induced expansion/contraction,improved flowability, and the like).

The subject invention further relates to an olefin polymerizationcatalyst system formed from a solid titanium catalyst componentcomprising titanium and a catalyst support made from an inorganicmagnesium compound, an alcohol, a porous support having certain physicalcharacteristics, and optionally an internal electron donor; anorganoaluminum compound; and optionally an organosilicon compound(external electron donor), or a derivative derived from any of thesegroups; and a polymerization process which comprises polymerizing orcopolymerizing olefins in the presence of the polymerization catalystsystem described above.

Generally speaking, the solid titanium catalyst component is made bycontacting at least one inorganic magnesium compound with an alcohol inan organic medium; then contacting a porous support having certainphysical characteristics with the inorganic magnesium compound-alcoholproduct. After the inorganic magnesium compound-alcohol product isimpregnated on the porous support, an inorganic titanium compound andoptionally an internal electron donor are contacted with the impregnatedporous support. The desirable and beneficial properties of the solidtitanium catalyst component are not obtained when the alcohol, inorganicmagnesium compound, porous support having certain physicalcharacteristics, and inorganic titanium compound are otherwise notemployed.

The porous support has physical characteristics that lead to thefabrication of desirable and beneficial solid titanium catalystcomponents. That is, the porous support directly contributes to many ofthe beneficial properties of the solid titanium catalyst component inparticular and olefin catalyst system generally. In this connection, thesupport is a necessary feature of the invention. Specifically the poroussupport has at least one of a certain specific surface area, a certainpore volume, and a certain median particle size to contribute to thedesirable and beneficial properties of the solid titanium catalystcomponents. The porous support may have at least two of a certainspecific surface area, a certain pore volume, and a certain medianparticle size to contribute to the desirable and beneficial propertiesof the solid titanium catalyst components. The porous support may haveall three of a certain specific surface area, a certain pore volume, anda certain median particle size to contribute to the desirable andbeneficial properties of the solid titanium catalyst components.

In one embodiment, the specific surface area of the porous support isabout 100 m²/g or more and about 2,000 m²/g or less. In anotherembodiment, the specific surface area of the porous support is about 200m²/g or more and about 1,500 m²/g or less. In yet another embodiment,the specific surface area of the porous support is about 300 m²/g ormore and about 1,000 m²/g or less. Specific surface area can bedetermined using conventional techniques involving nitrogen absorptionisotherms such as using ASTM D3663-03 entitled “Standard Test Method forSurface Area of Catalysts and Catalyst Carriers” which is incorporatedby reference herein.

In one embodiment, the pore volume of the porous support is about 0.2cc/g or more and about 5 cc/g or less. In another embodiment, the porevolume of the porous support is about 0.3 cc/g or more and about 4 cc/gor less. In yet another embodiment, the pore volume of the poroussupport is about 0.5 cc/g or more and about 3 cc/g or less. Pore volumemay be determined by a nitrogen absorption test, such as using a methodin accordance with the analysis method outlined in ASTM D 4641-88entitled “Standard practice for calculation of pore size distributionsof catalysts from nitrogen absorption isotherms” which is incorporatedby reference herein.

In one embodiment, the median particle size (by volume) of the poroussupport is about 1 micron or more and about 200 microns or less. Inanother embodiment, the median particle size (by volume) of the poroussupport is about 5 microns or more and about 150 microns or less. In yetanother embodiment, the median particle size (by volume) of the poroussupport is about 10 microns or more and about 100 microns or less.Median particle size can be determined using customary techniques suchas using conventional methods and devices for measuring particle sizes.For the purposes of this invention, median particle size is determinedby conventional laser diffraction techniques using a Malvern Instrument.Generally speaking, light from a laser is directed at a cloud ofparticles suspended in a transparent medium. The particles scatter thelight, and smaller particles scattering the light at larger angles thanbigger particles. The scattered light is measured by a series ofphotodetectors placed at different angles.

The porous support material can be obtained from a plethora ofcommercial sources, including Grace Davison, Ineos, Engelhard, and thelike.

The porous support contains and/or is made of a material that cansupport titanium and an inorganic magnesium compound-alcohol product(and optionally an internal electron donor). General examples of poroussupport materials include metal oxides and other materials havinghydroxyl groups on the surface. Specific examples of porous supportmaterials include silica, alumina, alumina-silicates, ceria, zeolites,clay, zirconia, titania, zinc oxide, and the like.

The inorganic magnesium compounds used in the preparation of the solidtitanium catalyst component include, for example, magnesium halides. Bythe term inorganic, the inorganic magnesium compounds do not contain acarbon atom (such as an organometallic magnesium compound such as alkoxymagnesiums). Examples of inorganic magnesium compounds include magnesiumchloride, magnesium bromide, magnesium iodide and magnesium fluoride,hydrates of any of the magnesium halides, and the like.

The alcohol facilitates dissolving the inorganic magnesium compound bycombining with the inorganic magnesium compound to provide an adduct.General examples of alcohols include primary alcohols, alkyl alcohols,alkenyl alcohols, and aromatic alcohols. In these general examples, thealkyl, alkenyl, aromatic groups contain from 1 to about 12 carbon atoms.In another embodiment, the alkyl, alkenyl, aromatic groups contain fromabout 2 to about 8 carbon atoms. Examples of alcohols include methanol,ethanol, n-propanol, isopropanol, n-butanol, iso-butanol, t-butanol,n-pentanol, iso-pentanol, hexanol, 2-ethylhexanol, decanol,cyclohexanol, phenol, and the like.

The organic medium in which the inorganic magnesium compound and alcoholare contacted include one or more organic solvents and/or organicliquids. Preferably the organic solvent is capable of permitting andfacilitating the formation of an adduct from the inorganic magnesiumcompound and the alcohol. Examples of organic solvents include alkanessuch as butane, pentane, hexane, heptane, octanes, decane, kerosene,cyclopentane, cyclohexane, and cyclooctane; aromatic hydrocarbons suchas benzene, toluene, xylene, ethylbenzene, and naphthalenes; oxygencontaining compounds such as alcohols and glycols; ketones; esters;ethers; and the like.

A suitable amount of the organic medium is employed when the inorganicmagnesium compound and alcohol are contacted to form the magnesiumalcohol adduct. In one embodiment, when contacting the inorganicmagnesium compound and alcohol, the molar ratio of the organic medium toinorganic magnesium compound is about 1:1 to about 50:1. In anotherembodiment, when contacting the inorganic magnesium compound andalcohol, the molar ratio of the organic medium to inorganic magnesiumcompound is about 2:1 to about 30:1. In yet another embodiment, whencontacting the inorganic magnesium compound and alcohol, the molar ratioof the organic medium to inorganic magnesium compound is about 3:1 toabout 10:1.

The inorganic magnesium compound, alcohol, and organic medium can becombined in any order (all at once; the inorganic magnesium compound andthe organic medium initially combined, followed by separate,semi-simultaneous, or simultaneous additions of the alcohol; or thealcohol and the organic medium initially combined, followed by additionof the inorganic magnesium compound). When the components are not addedat the same time, the mixture as it is formed may be heated to discretetemperatures after adding some or all of the components (that is,between adding components).

The mixture of the magnesium compound, alcohol, and organic medium (orany submixture containing less than all of these components) may beheated above room temperature for a suitable amount of time. In oneembodiment, the mixture or a submixture is heated to a temperature fromabout 40° C. to about 200° C. In another embodiment, the mixture or asubmixture is heated to a temperature from about 60° C. to about 140° C.In yet another embodiment, the mixture or a submixture is heated to atemperature from about 80° C. to about 120° C. In one embodiment, themixture or a submixture is heated for a period of time from about 10minutes to about 15 hours. In another embodiment, the mixture or asubmixture is heated for a period of time from about 30 minutes to about10 hours. In yet another embodiment, the mixture or a submixture isheated for a period of time from about 1 hour to about 4 hours.

Suitable relative amounts of the inorganic magnesium compound andalcohol are contacted to form the magnesium alcohol adduct. In oneembodiment, when contacting the inorganic magnesium compound andalcohol, the molar ratio of alcohol to inorganic magnesium compound isabout 0.1:1 to about 1:0.1. In another embodiment, when contacting theinorganic magnesium compound and alcohol, the molar ratio of alcohol toinorganic magnesium compound is about 0.25:1 to about 1:0.25. In yetanother embodiment, when contacting the inorganic magnesium compound andalcohol, the molar ratio of alcohol to inorganic magnesium compound isabout 0.5:1 to about 1:0.5.

The magnesium alcohol adduct may be recovered from the mixture by anysuitable means, such as precipitation techniques. In one embodiment,however, the magnesium alcohol adduct is not formed or recovered usingspray drying. In another embodiment, the magnesium alcohol adduct is notdealcoholed. The magnesium alcohol adduct is then contacted with theporous support in the same or different organic medium to impregnate theporous support with the magnesium alcohol adduct. Alternatively, if themagnesium alcohol adduct is not recovered from the mixture, themagnesium alcohol adduct is contacted with the porous support in theorganic medium in which the magnesium alcohol adduct is formed toimpregnate the porous support with the magnesium alcohol adduct.

The impregnated support may be recovered from the organic medium by anysuitable means, such as precipitation techniques, filtering techniques,and the like. The solid titanium catalyst component may be prepared bycontacting the impregnated support with an inorganic titanium compound.Alternatively, if the impregnated support is not recovered from theorganic medium, an inorganic titanium compound is contacted with theimpregnated support in the organic medium to form the solid titaniumcatalyst component.

The inorganic titanium compound used in the preparation of the solidtitanium catalyst component is, for example, an inorganic tetravalenttitanium compound represented by Formula (I)Ti(R)_(g)X_(4−g)  (I)wherein each R independently represents a non-halogen inorganic group, Xrepresents a halogen atom, and 0≦g≦4. By the term inorganic, theinorganic titanium compounds do not contain a carbon atom (such as anorganometallic titanium compounds such as alkoxy titaniums and alkoxytitanium halides). Specific examples of the inorganic titanium compoundinclude titanium tetrahalides such as TiCl₄, TiBr₄ and TiI₄. Thesetitanium compounds may be used individually or in a combination of twoor more. They may be used as dilutions in hydrocarbon compounds orhalogenated hydrocarbons.

When preparing the solid titanium catalyst component, an internalelectron donor is optionally used/added. Generally speaking, when thedesired olefin is or contains polypropylene, an internal electron donoris typically used. Internal electron donors, for example,oxygen-containing electron donors such as alcohols, certainorganosilicon compounds, phenols, ketones, aldehydes, carboxylic acids,organic or inorganic acid esters, ethers, acid amides and acidanhydrides, and nitrogen-containing electron donors such as ammonia,amines, nitriles and isocyanates.

Specific examples include organic acid esters having 2 to about 30carbon atoms such as methyl formate, ethyl acetate, vinyl acetate,propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate,methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate,ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, dibutylmaleate, diethyl butylmalonate, diethyl dibutylmalonate, ethylcyclohexanecarboxylate, diethyl 1,2-cyclohexanedicarboxylate,di-2-ethylhexyl 1,2-cyclohexanedicarboxylate, methyl benzoate, ethylbenzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexylbenzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyltoluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, ethylanisate, ethyl ethoxybenzoate, dimethyl phthalate, diethyl phthalate,dipropyl phthalate, diisopropyl phthalate, dibutyl phthalate, diisobutylphthalate, dioctyl phthalate, gamma-butyrolactone, delta-valerolactone,coumarine, phthalide and ethylene carbonate; inorganic acid esters suchas ethyl silicate, butyl silicate, vinyltriethoxysilane,phenyltriethoxysilane and diphenyldiethoxysilane; acid halides having 2to about 15 carbon atoms such as acetyl chloride, benzoyl chloride,tolyl chloride, anisoyl chloride and phthaloyl dichloride; ethers having2 to about 20 carbon atoms such as methyl ether, ethyl ether, isopropylether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenylether; acid amides such as acetamide, benzamide and toluamide; acidanhydrides such as benzoic anhydride and phthalic anhydride, amines suchas methylamine, ethylamine, diethylamine, tributylamine, piperidine,tribenzylamine, aniline, pyridine, picoline andtetramethylethylenediamine; and nitriles such as acetonitrile,benzonitrile and tolunitrile.

Esters may also be employed as internal electron donors for use with thetitanium catalyst component. Examples of these esters are compoundsrepresented by the following formulae

wherein R¹ represents a substituted or unsubstituted hydrocarbon group,and R², R⁵ and R⁶ represent a hydrogen atom or a substituted orunsubstituted hydrocarbon group, R³ and R⁴ represent a hydrogen atom ora substituted or unsubstituted hydrocarbon group, at least one of themis preferably a substituted or unsubstituted hydrocarbon group, and R³and R⁴ may be linked to each other. In one embodiment, the substitutedor unsubstituted hydrocarbon groups contain from 1 to about 30 carbonatoms.

Examples of the substituted hydrocarbon groups for R¹ through R⁵ arehydrocarbon groups having groups containing hetero atoms such as N, Oand S, for example, C—O—C, COOR, COOH, OH, SO₃H, —C—N—C— and NH₂.Especially preferred are diesters of dicarboxylic acids in which atleast one of R¹ and R² is an alkyl group having at least about 2 carbonatoms.

Specific examples of polycarboxylic acid esters include aliphaticpolycarboxylic acid esters such as diethyl succinate, dibutyl succinate,diethyl methylsuccinate, dipropylsuccinate, dipentylsuccinate,dihexylsuccinate, dioctylsuccinate, didecylsuccinate,butlyoctylsuccinate, didodecylsuccinate, and other alkylsuccinates,diisobutyl alpha-methylglutarate, diethyl malonate, dibutyl malonate,diethyl methylmalonate, diethyl ethylmalonate, diethylisopropylmalonate, diethyl butyl malonate, diethyl phenylmalonate,diethyl diethylmalonate, diethyl allylmalonate, diethyldiisobutylmalonate, diethyl di-n-butylmalonate, dimethyl maleate,diethyl maleate, monooctyl maleate, dioctyl maleate, di-n-butyl maleate,di-iso-butyl maleate, dibutyl butylmaleate, diethyl butylmaleate,diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate,diisopropyl beta-methylglutarate, diallyl ethylsuccinate,di-2-ethylhexyl fumarate, diethyl itaconate, dibutyl itaconate, dioctylcitraconate and dimethyl citraconate; alicyclic polycarboxylic acidesters such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate and Nadic acid,diethyl ester; aromatic polycarboxylic acid esters such as monoethylphthalate, dimethyl phthalate, methylethyl phthalate, monoisobutylphthalate, mono-n-butyl phthalate, diethyl phthalate, ethlisobutylphthalate, ethyl-n-butyl phthalate, di-n-propyl phthalate, diisopropylphthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptylphthlate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, di-iso-octylphthalate, dineopentyl phthalate, didecyl phthalate, benzylbutylphthalate, diphenyl phthalate, diethyl naphthalenedicarboxylate, dibutylnaphthlenedicarboxylate, triethyl trimelliatate, dibutyl trimellitate,triethyl hemimellitate, tributyl hemimellitate, tetraethylpyromellitate, tetrabutyl pyromellitate, diethyl1,2-cyclohexane-dicarboxylate, anddibutyl-1,2-cyclohexane-dicarboxylate; and heterocyclic polycarboxylicacid esters such as 3,4-furanedicarboxylic acid esters. Specificexamples of the polyhydroxy compound esters may include1,2-diacetoxybenzene, 1-methyl-2,3-diacetoxybenzene,2-methyl-2,3-diacetoxybenzene, 2,8-d iacetoxynaphthalene, ethyleneglycol dipivalate and butanediol pivalate. Specific examples of thehydroxy-substituted carboxylic acid esters are benzoylethyl salicylate,acetylisobutyl salicylate and acetylmethyl salicylate.

Long-chain dicarboxylic acid esters, such as diethyl adipate, diisobutyladipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacateand di-2-ethylhexyl sebacate, may also be used as the polycarboxylicacid esters that can be included in the titanium catalyst component.Among these polyfunctional esters, compounds having the skeletons givenby the above general formulae are preferred. Also preferred are estersformed between phthalic acid, maleic acid or substituted malonic acidand alcohols having at least about 2 carbon atoms, diesters formedbetween phthalic acid and alcohols having at least about 2 carbon atomsare especially preferred.

Another group of internal electron donors that can be included in thetitanium catalyst component are monocarboxylic acid esters representedby RCOOR′ where R and R′ are hydrocarboyl groups that may have asubstituent, and at least one of them is a branched (includingalicyclic) or ring-containing aliphatic group. Specifically, at leastone of R and R′ may be (CH₃)₂CH—, C₂H₅CH(CH₃)—, (CH₃)₂CHCH₂—, (CH₃)₃C—,C₂H₅CH—, (CH₃)CH₂—, cyclohexyl, methylbenzyl, para-xylyl, acrylic, andcarbonylbenzyl. If either one of R and R′ is any of the above-describedgroup, the other may be the above group or another group such as alinear or cyclic group. Specific examples of the monocarboxylic acidesters include monoesters of dimethylacetic acid, trimethylacetic acid,alpha-methylbutyric acid, beta-methylbutyric acid, methacrylic acid andbenzoylacetic acid; and monocarboxylic acid esters formed with alcoholssuch as methanol, ethanol, isopropanol, isobutanol and tert-butanol.

The internal electron donors may be used individually or in combination.In employing the internal electron donor, they do not have to be useddirectly as starting materials, but compounds convertible to theelectron donors in the course of preparing the titanium catalystcomponents may also be used as the starting materials.

The solid titanium catalyst component may be formed by contacting themagnesium containing catalyst support, the titanium compound, and theinternal electron donor by known methods used to prepare a highly activetitanium catalyst component from a magnesium support, a titaniumcompound, and an electron donor.

Several examples of the method of producing the solid titanium catalystcomponent are briefly described below.

(1) The magnesium alcohol adduct impregnated support optionally with theinternal electron donor, is contacted with the inorganic titaniumcompound in the liquid phase.

(2) The magnesium alcohol adduct impregnated support and the inorganictitanium compound are contacted in the presence of the optional internalelectron donor to precipitate a solid titanium complex.

(3) The reaction product obtained in (2) is further reacted with aninorganic titanium compound.

(4) The reaction product obtained in (1) or (2) is further contactedwith the optional internal electron donor and the inorganic titaniumcompound.

(5) The product obtained in (1) to (4) is treated with a halogen, ahalogen compound or an aromatic hydrocarbon.

(6) The magnesium alcohol adduct impregnated support is contacted withthe optional internal electron donor, the inorganic titanium compoundand/or a halogen-containing hydrocarbon.

(7) The magnesium alcohol adduct impregnated support is contacted withthe inorganic titanium compound in the liquid phase, filtered andwashed. The product is further contacted with the optional internalelectron donor and the inorganic titanium compound, then activated withadditional inorganic titanium compound in an organic medium.

In embodiments of making the solid titanium catalyst component accordingto examples (2), (3), (4) and (5), the magnesium alcohol adductimpregnated support solution is mixed with liquid titanium tetrahalideto form a solid precipitate in the optional presence of an auxiliaryprecipitant. A polycarboxylic acid ester may be added before, during orafter the precipitation of the solids and loaded on the solid.

The process of solids precipitation can be carried out by adding liquidtitanium tetrahalide dropwise into a magnesium alcohol adductimpregnated support solution at low or room temperature to precipitateout solids immediately. An internal electron donor is optionally presentin the reaction system. The internal electron donor can be added eitherafter the magnesium alcohol adduct impregnated support solution isobtained or together with the magnesium alcohol adduct impregnatedsupport.

To facilitate obtaining uniform solid particles, the process ofprecipitation can be carried out slowly. When adding inorganic titaniumcompound dropwise at low or room temperature is applied, the process maytake place over a period from about 1 hour to about 6 hours.

The solid precipitate is first separated from the mixture. In the solidprecipitate thus obtained may be entrained a variety of complexes andimpurities, so that further treatment may in some instances benecessary.

The solid precipitate is washed with an inert diluent and then treatedwith titanium tetrahalide or a mixture of titanium tetrahalide and aninert diluent. The titanium tetrahalide used in this act is identical toor different with the inorganic titanium compound used. The amount oftitanium tetrahalide used is from about 1 to about 20 moles, such asfrom about 2 to about 15 moles, per mole of magnesium in the poroussupport. The treatment temperature ranges from about 50° C. to about150° C., such as from about 60° C. to about 100° C. If a mixture oftitanium tetrahalide and inert diluent is used to treat the solidprecipitate, the volume % of titanium tetrahalide in the treatingsolution is from about 10% to about 100%, the rest being an inertdiluent.

The treated solids can be further washed with an inert diluent to removeineffective titanium compounds and other impurities. The inert diluentherein used can be hexane, heptane, octane, 1,2-dichloroethane, benzene,toluene, xylenes, and other hydrocarbons.

In one embodiment, particularly embodiments following example (2)described above, the solid catalyst component has the following chemicalcomposition: titanium, from about 1 to about 7 wt %; magnesium, fromabout 3 to about 15 wt %; halogen, from about 10 to about 40 wt %;optional internal electron donor, from about 0.5 to about 15 wt %; andporous support from about 40 to about 85 wt %.

The solid titanium catalyst component is a highly active catalystcomponent comprising titanium, a magnesium alcohol adduct, a poroussupport, and optionally an internal electron donor. The amounts of theingredients used in preparing the solid titanium catalyst component mayvary depending upon the method of preparation. In one embodiment, fromabout 0.01 to about 5 moles of the optional internal electron donor andfrom about 0.01 to about 500 moles of the inorganic titanium compoundare used per mole of the inorganic magnesium compound used to make thesolid titanium catalyst component. In another embodiment, from about0.05 to about 2 moles of the optional internal electron donor and fromabout 0.05 to about 300 moles of the inorganic titanium compound areused per mole of the inorganic magnesium compound used to make the solidtitanium catalyst component.

In one embodiment, in the solid titanium catalyst component, the atomicratio of halogen/titanium is from about 4 to about 200; the optionalinternal electron donor/titanium mole ratio is from about 0.01 to about10; and the magnesium/titanium atomic ratio is from about 1 to about100. In another embodiment, in the solid titanium catalyst component,the atomic ratio of halogen/titanium is from about 5 to about 100; theoptional internal electron donor/titanium mole ratio is from about 0.2to about 6; and the magnesium/titanium atomic ratio is from about 2 toabout 50.

In one embodiment, the size (diameter) of the solid titanium catalystcomponent formed in accordance with the present invention is from about10 microns to about 150 microns (on a 50% by volume basis). In anotherembodiment, the size (diameter) of the solid titanium catalyst componentis from about 20 microns to about 100 microns (on a 50% by volumebasis). In yet another embodiment, the size (diameter) of the solidtitanium catalyst component is from about 30 microns to about 80 microns(on a 50% by volume basis).

The solid titanium catalyst component may be used as a catalystcomponent for making polyolefins after being combined or diluted with aninorganic or organic compound such as a silicon compound, an aluminumcompound.

Methods of preparing the solid titanium catalyst component, which can beused in the subject invention so long as the porous support, an alcohol,an inorganic magnesium compound, and an inorganic titanium compound areused, are described in U.S. Pat. Nos. and U.S. Patent Publications:4,639,430; 5,064,799; 5,227,439; 5,244,854; 5,278,117; 5,633,419;5,661,097; and 5,798,314; which are hereby incorporated by reference inthis regard.

The catalyst system may contain at least one organoaluminum compound inaddition to the solid titanium catalyst component. Compounds having atleast one aluminum-carbon bond in the molecule can be used as theorganoaluminum compound. Examples of organoaluminum compounds includecompounds of the following Formula (II).R_(m) ⁷Al(OR⁸)_(n)H_(p)X_(q) ¹  (II)In Formula (II), R⁷ and R⁸ may be identical or different, and eachrepresent a hydrocarbon group usually having 1 to about 15 carbon atoms,preferably 1 to about 4 carbon atoms; X¹ represents a halogen atom,0≦q<3, 0≦p<3, 0≦n<3, and m+n+p+q=3.

Specific examples of the organoaluminum compounds represented by Formula(II) include trialkyl aluminums such as triethyl aluminum and tributylaluminum; trialkenyl aluminums such as triisoprenyl aluminum; dialkylaluminum alkoxides such as diethyl aluminum ethoxide and dibutylaluminum butoxide; alkyl aluminum sesquialkoxides such as ethyl aluminumsesquiethoxide and butyl aluminum sesquibutoxide; partially alkoxylatedalkyl aluminums having an average composition represented by R_(2.5)⁷Al(OR⁸)_(0.5); dialkyl aluminum halides such as diethyl aluminumchloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkylaluminum sesquihalides such as ethyl aluminum sesquichloride, butylaluminum sesquichloride and ethyl aluminum sesquibromide; partiallyhalogenated alkyl aluminums, for example alkyl aluminum dihalides suchas ethyl aluminum dichloride, propyl aluminum dichloride and butylaluminum dibromide; dialkyl aluminum hydrides such as diethyl aluminumhydride and dibutyl aluminum hydride; other partially hydrogenated alkylaluminum, for example alkyl aluminum dihyrides such as ethyl aluminumdihydride and propyl aluminum dihydride; and partially alkoxylated andhalogenated alkyl aluminums such as ethyl aluminum ethoxychloride, butylaluminum butoxychloride and ethyl aluminum ethoxybromide.

The organoaluminum compound catalyst component is used in the catalystsystem in an amount that the mole ratio of aluminum to titanium (fromthe solid catalyst component) is from about 5 to about 1,000. In anotherembodiment, the mole ratio of aluminum to titanium in the catalystsystem is from about 10 to about 700. In yet another embodiment, themole ratio of aluminum to titanium in the catalyst system is from about25 to about 400.

The catalyst system may optionally contain at least one organosiliconcompound in addition to the solid titanium catalyst component. Thisorganosilicon compound is sometimes termed an external electron donor.In instances where polypropylene is made as the olefin (or portion ofthe copolymer), the organosilicon compound/external electron donor isemployed. The organosilicon compound contains silicon having at leastone hydrocarbon ligand (hydrocarbon group). General examples ofhydrocarbon groups include alkyl groups, cycloalkyl groups,(cycloalkyl)methylene groups, alkene groups, aromatic groups, and thelike.

The organosilicon compound, when used as an external electron donorserving as one component of a Ziegler-Natta catalyst system for olefinpolymerization, contributes to the ability to obtain a polymer (at leasta portion of which is polyolefin) having a broad molecular weightdistribution and controllable crystallinity while retaining highperformance with respect to catalytic activity and the yield of highlystereoregular polymer.

The organosilicon compound is used in the catalyst system in an amountthat the mole ratio of the organoaluminum compound to the organosiliconcompound is from about 2 to about 90. In another embodiment, the moleratio of the organoaluminum compound to the organosilicon compound isfrom about 5 to about 70. In yet another embodiment, the mole ratio ofthe organoaluminum compound to the organosilicon compound is from about7 to about 35.

In one embodiment, the organosilicon compound is represented by Formula(III)R_(n) ⁹Si(OR¹⁰)_(4−n)  (III)wherein R⁹ and R¹⁰ represent a hydrocarbon group, and n is 0≦n<4.Specific examples of the organosilicon compound of Formula (III) includetrimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane,dimethyldiethoxysilane, diisopropyldimethoxysilane,t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane,t-amylmethyldiethoxysilane, diphenyldimethoxysilane,phenylmethyldimethoxysilane, diphenyldiethoxysilane,bis-o-tolyldimethoxysilane, bis-m-tolyidimethoxysilane,bis-p-tolyldimethoxysilane, bis-p-totyldiethoxysilane,bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane,cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane,ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane,methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane,decyltriethoxysilane, phenyltrimethoxysilane,gamma-chloropropyltrimethoxysilane, methyltriethoxysilane,ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane,n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane,gamma-aminopropyltriethoxysilane, chlorotriethoxysilane,ethyltriisopropoxysilane, vinyltributoxysilane,cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,2-norbornanetrimethoxysilane, 2-norboranetriethoxysilane,2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate,trimethylphenoxysilane, methyltriallyloxysilane,vinyltris(beta-methoxyethoxysilane), vinyltriacetoxysilane, anddimethyltetraethoxydisiloxane.

In another aspect of the subject invention, the organosilicon compoundis represented by Formula (IV)SiR¹¹R_(m) ¹²(OR¹³)_(3−m)  (IV)In the above Formula (IV), 0≦m<3, such as 0≦m≦2; and R¹¹ represents acyclopropyl group, cyclobutyl group, cyclopentyl group, a cyclopentenylgroup, a cyclopentadienyl group, cyclohexyl group, or a derivative ofany of these. The derivative may preferably be, for example, acyclopentyl group substituted by 1 to about 4 alkyl groups having 1 toabout 4 carbon atoms, an alkyl group having 2 to about 4 carbon atomssubstituted by a cyclopentyl group which may be substituted by 1 toabout 4 alkyl groups having 1 to about 4 carbon atoms, a cyclopentenylgroup substituted by 1 to about 4 alkyl groups having 1 to about 4carbon atoms, a cyclopentadienyl group substituted by 1 to about 4 alkylgroups having 1 to about 4 carbon atoms, or an indenyl, indanyl,tetrahydroindenyl or fluorenyl group which may be substituted by 1 toabout 4 alkyl groups having 1 to about 4 carbon atoms.

Specific examples of the group R¹¹ include cyclopropyl, cyclobutyl,cyclopentyl, 2-methylcyclopentyl, 3-methylcyclopentyl,2-ethylcyclopentyl, 3-propylcyclopentyl, 3-isopropylcyclopentyl,3-butylcyclopentyl, 3-tertiary butyl cyclopentyl,2,2-dimethylcyclopentyl, 2,3-dimethylcyclopentyl,2,5-dimethylcyclopentyl, 2,2,5-trimethylcyclopentyl,2,3,4,5-tetramethylcyclopentyl, 2,2,5,5-tetramethylcyclopentyl,1-cyclopentylpropyl, 1-methyl-1-cyclopentylethyl, cyclopentenyl,2-cyclopentenyl, 3-cyclopentenyl, 2-methyl-1-cyclopentenyl,2-methyl-3-cyclopentenyl, 3-methyl-3-cyclopentenyl,2-ethyl-3-cyclopentenyl, 2,2-dimethyl-3-cyclopentenyl,2,5-dimethyl-3-cyclopentenyl, 2,3,4,5-tetramethyl-3-cyclopentenyl,2,2,5,5-tetramethyl-3-cyclopentenyl, 1,3-cyclopentadienyl,2,4-cyclopentadienyl, 1,4-cyclopentadienyl,2-methyl-1,3-cyclopentadienyl, 2-methyl-2,4-cyclopentadienyl,3-methyl-2,4-cyclopentadienyl, 2-ethyl-2,4-cyclopentadienyl,2-dimethyl-2,4-cyclopentadienyl, 2,3-dimethyl-2,4-cyclopentadienyl,2,5-dimethyl-2,4-cyclopentadienyl,2,3,4,5-tetramethyl-2,4-cyclopentadienyl, indenyl, 2-methylindenyl,2-ethylindenyl, 2-indenyl, 1-methyl-2-indenyl, 1,3-dimethyl-2-indenyl,indanyl, 2-methylindanyl, 2-indanyl, 1,3-dimethyl-2-indanyl,4,5,6,7-tetrahydroindenyl, 4,5,6,7-tetrahydro-2-indenyl,4,5,6,7-tetrahydro-1-methyl-2-indenyl,4,5,6,7-tetrahydro-1,3-dimethyl-2-indenyl, fluorenyl groups, cyclohexyl,methylcyclohexyls, ethylcyclohexyls, propylcyclohexyls,isopropylcyclohexyls, n-butylcyclohexyls, tertiary-butyl cyclohexyls,dimethylcyclohexyls, and trimethylcyclohexyls.

In Formula (IV), R¹² and R¹³ are identical or different and eachrepresents a hydrocarbon. Examples of R¹² and R¹³ are alkyl, cycloalkyl,aryl and aralkyl groups having 3 or more carbon atoms. Furthermore, R¹¹and R¹² may be bridged by an alkyl group, etc. General examples oforganosilicon compounds are those of Formula (IV) in which R¹¹ is acyclopentyl group, R¹² is an alkyl group such as methyl or a cyclopentylgroup, and R¹³ is an alkyl group, particularly a methyl or ethyl group.

Specific examples of organosilicon compounds of Formula (IV) includetrialkoxysilanes such as cyclopropyltrimethoxysilane,cyclobutyltrimethoxysilane, cyclopentyltrimethoxysilane,2-methylcyclopentyltrimethoxysilane,2,3-dimethylcyclopentyltrimethoxysilane,2,5-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,cyclopentenyltrimethoxysilane, 3-cyclopentenyltrimethoxysilane,2,4-cyclopentadienyltrimethoxysilane, indenyltrimethoxysilane andfluorenyltrimethoxysilane; dialkoxysilanes such asdicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane,bis(3-tertiary butylcyclopentyl)dimethoxysilane,bis(2,3-dimethylcyclopentyl)dimethoxysilane,bis(2,5-dimethylcyclopentyl)dimethoxysilane,dicyclopentyidiethoxysilane, dicyclobutyldiethoxysilane,cyclopropylcyclobutyidiethoxysilane, dicyclopentenyidimethoxysilane,di(3-cyclopentenyl)dimethoxysilane,bis(2,5-dimethyl-3-cyclopentenyl)dimethoxysilane,di-2,4-cyclopentadienyldimethoxysilane,bis(2,5-dimethyl-2,4-cyclopentadienyl)dimethoxysilane,bis(1-methyl-1-cyclopentylethyl)dimethoxysilane,cyclopentylcyclopentenyidimethoxysilane,cyclopentylcyclopentadienyldimethoxysilane, diindenyldimethoxysilane,bis(1,3-dimethyl-2-indenyl)dimethoxysilane,cyclopentadienylindenyldimethoxysilane, difluorenyidimethoxysilane,cyclopentylfluorenyldimethoxysilane and indenylfluorenyldimethoxysilane;monoalkoxysilanes such as tricyclopentylmethoxysilane,tricyclopentenylmethoxysilane, tricyclopentadienylmethoxysilane,tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane,dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane,cyclopentyldimethylmethoxysilane, cyclopentyidiethylmethoxysilane,cyclopentyldimethylethoxysilane,bis(2,5-dimethylcyclopentyl)cyclopentylmethoxysilane,dicyclopentylcyclopentenylmethoxysilane,dicyclopentylcyclopentadienylmethoxysilane anddiindenylcyclopentylmethoxysilane; andethylenebis-cyclopentyldimethoxysilane.

In another aspect of the subject invention, the organosilicon compoundis a polyorganosilicon compound containing, as a monomer, any of theorganosilicon compounds described above.

Polymerization of olefins is carried out in the presence of the catalystsystems described above. Generally speaking, olefins are contacted withthe catalyst system described above under suitable conditions to formdesired polymer products. In one embodiment, the polymerization iscarried out by adding an olefin and the catalyst system to an inerthydrocarbon medium and reacting the olefin under suitable conditions ina reaction or polymerization zone. In another embodiment, the formationof impact copolymer is carried out using at least two polymerizationzones.

Specific examples of the inert hydrocarbon medium include aliphatichydrocarbons such as propane, butane, pentane, hexane, heptane, octane,decane, dodecane and kerosene; alicyclic hydrocarbons such ascyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbonssuch as benzene, toluene and xylene; halogenated hydrocarbons such asethylene chloride and chlorobenzene; and mixtures thereof. In thepolymerization, a liquid olefin may be used in place of part or thewhole of the inert hydrocarbon medium.

Examples of olefins that can be used in the main polymerization arealpha-olefins having 2 to 20 carbon atoms such as ethylene, propylene,1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-hexene,3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, 1-tetradecene,1-eicosene, and vinylcyclohexane. In the polymerization processes, thesealpha-olefins may be used individually or in any combination withanother olefin or other monomer. The resultant products are the polymersincluding one or more the olefin monomers.

In one embodiment, an olefin is homopolymerized, or two or more olefinsare copolymerized. In another one embodiment, copolymers made with thecatalyst system contain from about 50% to about 99% by weightpolyolefins and from about 1% to about 50% by weight comonomers (such asthermoplastic or elastomeric monomers). In another embodiment,copolymers made with the catalyst system contain from about 75% to about98% by weight polyolefins and from about 2% to about 25% by weightnon-olefin comonomers. Examples of comonomers include styrene,butadiene, acrylonitrile, acrylamide, alpha-methyl styrene,chlorostyrene, vinyl toluene, divinyl benzene, diallylphthalate, alkylmethacrylates and alkyl acrylates.

In one embodiment, polymerization employs a catalyst system containingthe titanium catalyst component in an amount from about 0.001 to about0.75 millimole calculated as Ti atom per liter of the volume of thepolymerization zone, the organoaluminum compound in an amount from about1 to about 2,000 moles per mole of titanium atoms in the titaniumcatalyst component, and the optional organosilicon compound (externaldonor) in an amount from about 0.001 to about 10 moles calculated as Siatoms in the organosilicon compound per mol of the metal atoms in theorganoaluminum compound (when present). In another embodiment,polymerization employs a catalyst system containing the titaniumcatalyst component in an amount from about 0.005 to about 0.5 millimolecalculated as Ti atom per liter of the volume of the polymerizationzone, the organoaluminum compound in an amount from about 5 to about 500moles per mole of titanium atoms in the titanium catalyst component, andthe optional organosilicon compound in an amount from about 0.01 toabout 2 moles calculated as Si atoms in the organosilicon compound permol of the metal atoms in the organoaluminum compound. In yet anotherembodiment, polymerization employs a catalyst system optionallycontaining the organosilicon compound in an amount from about 0.05 toabout 1 mole calculated as Si atoms in the organosilicon compound permol of the metal atoms in the organoaluminum compound.

The use of hydrogen at the time of polymerization promotes andcontributes to control of the molecular weight of the resulting polymer,and the polymer obtained may have a high melt flow rate.

In one embodiment, the polymerization temperature is from about 0° C. toabout 200° C. In another embodiment, the polymerization temperature isfrom about 20° C. to about 100° C. In one embodiment, the polymerizationpressure is typically from about subatmospheric pressure (about 0.1 baror more) to about 100 bar. In another embodiment, the polymerizationpressure is typically from about 2 bar to about 75 bar. The mainpolymerization may be carried out batchwise, semi-continuously orcontinuously. The polymerization may also be carried out in two or morestages under different reaction conditions. The polymerization of anolefin is carried out usually in the gaseous, suspension phase (in aslurry), or liquid phase.

The olefin polymer so obtained may be a homopolymer, a random copolymer,a block copolymer or an impact copolymer. The impact coplymer containsan intimate mixture of a polyolefin homopolymer and a polyolefin rubber.For example, propylene and an ethylene rubber may be formed in tworeactors coupled in series to form an impact copolymer. Examples ofpolyolefin rubbers include ethylene propylene rubbers (EPR) such asethylene propylene methylene copolymer rubber (EPM) and ethylenepropylene diene methylene terpolymer rubber (EPDM). Examples ofpolyethylenes include high density polyethylene and linear low densitypolyethylene.

Block copolymerization of propylene or ethylene and another olefin maybe carried out in two stages. The polymerization in a first stage may bethe homopolymerization of propylene or the copolymerization of propylenewith the other olefin. In one embodiment, the amount of the monomerspolymerized in the first stage is from about 50 to about 95% by weight.In another embodiment, the amount of the monomers polymerized in thefirst stage is from about 60 to about 90% by weight. This first stagepolymerization may, as required be carried out in two or more stagesunder the same or different polymerization conditions.

In one embodiment, the polymerization in a second stage is desirablycarried out such that the mole ratio of propylene or ethylene to theother olefin(s) is from about 10/90 to about 90/10. In anotherembodiment, the polymerization in a second stage is desirably carriedout such that the mole ratio of propylene or ethylene to the otherolefin(s) is from about 20/80 to about 80/20. In yet another embodiment,the polymerization in a second stage is desirably carried out such thatthe mole ratio of propylene or ethylene to the other olefin(s) is fromabout 30/70 to about 70/30. Producing a crystalline polymer or copolymerof another olefin may be provided in the second polymerization stage.

The catalysts/methods of the subject invention can in some instanceslead to the production of polyolefins including ICPs having xylenesolubles (XS) from about 0.5% to about 10%. In another embodiment,polyolefins having xylene solubles (XS) from about 2% to about 7% areproduced in accordance with the present invention. In yet anotherembodiment, polyolefins having xylene solubles (XS) from about 3% toabout 6% are produced in accordance with the present invention. XSrefers to the percent of solid polymer that dissolves into xylene. A lowXS % value generally corresponds to a highly isotactic polymer (i.e.,higher crystallinity), whereas a high XS % value generally correspondsto a low isotactic polymer.

The catalysts/methods of the subject invention can in some instanceslead to the production of polyolefins including ICPs having bulkdensities (BD) of at least about 0.3 cc/g. For example, in oneembodiment, a polyolefin product has a BD of at least about 0.35 cc/g.In another embodiment, a polyolefin product has a BD of at least about0.38 cc/g.

The subject invention can lead to the production of polyolefinsincluding polyethylene, polypropylene, propylene block copolymers, andimpact copolymers including polypropylene based impact copolymers havingone or more of excellent melt-flowability, moldability, desirablebalance between rigidity and elasticity, good stereospecific control,good control over size, shape, size distribution, and molecular weightdistribution, impact strength and impact strength with a high catalyticefficiency and/or good operability. Employing the catalyst systemscontaining solid titanium catalyst component made from an inorganictitanium compound, an inorganic magnesium compound, an alcohol, andsolid, porous support having certain physical characteristics yieldscatalysts simultaneously having high catalytic efficiency and one ormore of excellent melt-flowability, extrudability, moldability,rigidity-elasticity, impact strength and impact strength.

The olefin polymer obtained by using the catalyst system may have a verysmall amount of an amorphous polymer component and therefore a smallamount of a hydrocarbon-soluble component. Accordingly, a film moldedfrom this resultant polymer may have low surface tackiness.

The polyolefin obtained by the polymerization process is excellent inparticle size distribution, particle diameter and bulk density, and thecopolyolefin obtained has a narrow composition distribution. In animpact copolymer, excellent fluidity, low temperature resistance, and adesired balance between stiffness and elasticity can be obtained.

Examples of systems for polymerizing olefins are now described.Referring to FIG. 1, a high level schematic diagram of a system 10 forpolymerizing olefins is shown. Inlet 12 is used to introduce into areactor 14 catalyst system components, olefins, optional comonomers,hydrogen gas, fluid media, pH adjusters, surfactants, and any otheradditives. Although only one inlet is shown, many often are employed.Reactor 14 is any suitable vehicle that can polymerize olefins. Examplesof reactors 14 include a single reactor, a series of two or morereactors, slurry reactors, fixed bed reactors, gas phase reactors,fluidized gas reactors, loop reactors, multizone circulating reactors,and the like. Once polymerization is complete, or as polyolefins areproduced, the polymer product is removed from the reactor 14 via outlet16 which leads to a collector 18. Collector 18 may include downstreamprocessing, such as heating, extrusion, molding, and the like.

Referring to FIG. 2, a schematic diagram of a multizone circulatingreactor 20 that can be employed as the reactor 14 in FIG. 1 or reactor44 in FIG. 3 for making polyolefins. The multizone circulating reactor20 substitutes a series of separate reactors with a single reactor loopthat permits different gas phase polymerization conditions in the twosides due to use of a liquid barrier. In the multizone circulatingreactor 20, a first zone starts out rich in olefin monomer, andoptionally one or more comonomers. A second zone is rich in hydrogengas, and a high velocity gas flow divides the growing resin particlesout loosely. The two zones produce resins of different molecular weightand/or monomer composition. Polymer granules grow as they circulatearound the loop, building up alternating layers of each polymer fractionin an onion like fashion. Each polymer particle constitutes an intimatecombination of both polymer fractions.

In operation, the polymer particles pass up through the fluidizing gasin an ascending side 24 of the loop and come down through the liquidmonomer on a descending side 26. The same or different monomers (andagain optionally one or more comonomers) can be added in the two reactorlegs. The reactor uses the catalyst systems described above.

In the liquid/gas separation zone 30, hydrogen gas is removed to cooland recirculate. Polymer granules are then packed into the top of thedescending side 26, where they then descend. Monomers are introduced asliquids in this section. Conditions in the top of the descending side 26can be varied with different combinations and/or proportions of monomersin successive passes.

Referring to FIG. 3, a high level schematic diagram of another system 40for polymerizing olefins is shown. This system is ideally suited to makeimpact copolymer. A reactor 44, such as a single reactor, a series ofreactors, or the multizone circulating reactor is paired with a gasphase or fluidized bed reactor 48 downstream containing the catalystsystems described above to make impact copolymers with desirable impactto stiffness balance or greater softness than are made with conventionalcatalyst systems. Inlet 42 is used to introduce into the reactor 44catalyst system components, olefins, optional comonomers, hydrogen gas,fluid media, pH adjusters, surfactants, and any other additives.Although only one inlet is shown, many often are employed. Throughtransfer means 46 the polyolefin made in the first reactor 44 is sent toa second reactor 48. Feed 50 is used to introduce catalyst systemcomponents, olefins, optional comonomers, fluid media, and any otheradditives. The second reactor 48 may or may not contain catalyst systemcomponents. Again, although only one inlet is shown, many often areemployed. Once the second polymerization is complete, or as impactcopolymers are produced, the polymer product is removed from the secondreactor 48 via outlet 52 which leads to a collector 54. Collector 54 mayinclude downstream processing, such as heating, extrusion, molding, andthe like. At least one of the first reactor 44 and second reactor 48contains catalyst systems in accordance with the invention.

When making an impact copolymer, polypropylene can be formed in thefirst reactor while an ethylene propylene rubber can be formed in thesecond reactor. In this polymerization, the ethylene propylene rubber inthe second reactor is formed with the matrix (and particularly withinthe pores) of the polypropylene formed in the first reactor.Consequently, an intimate mixture of an impact copolymer is formed,wherein the polymer product appears as a single polymer product. Such anintimate mixture cannot be made by simply mixing a polypropylene productwith an ethylene propylene rubber product.

Although not shown in any of the figures, the systems and reactors canbe controlled, optionally with feedback based on continuous orintermittent testing, using a processor equipped with an optional memoryand controllers. For example, a processor may be connected to one ormore of the reactors, inlets, outlets, testing/measuring systems coupledwith the reactors, and the like to monitor and/or control thepolymerization process, based on preset data concerning the reactions,and/or based on testing/measuring data generated during a reaction. Thecontroller may control valves, flow rates, the amounts of materialsentering the systems, the conditions (temperature, reaction time, pH,etc.) of the reactions, and the like, as instructed by the processor.The processor may contain or be coupled to a memory that contains dataconcerning various aspects of the polymerization process and/or thesystems involved in the polymerization process.

The following examples illustrate the present invention. Unlessotherwise indicated in the following examples and elsewhere in thespecification and claims, all parts and percentages are by weight, alltemperatures are in degrees Centigrade, and pressure is at or nearatmospheric pressure.

EXAMPLE 1

10 g of magnesium chloride is dissolved in the 28 ml of ethanol and 200ml hexane. 20 g of silica (Grace Davison SYLOPOL 2229) is slurried inmagnesium chloride solution for 1 hour. The slurry is cooled down to−20° C. and 50 g of titanium tetrachloride is added. The temperature isincreased to 80° C. and 5 ml diisobutyl phthalate (DIBP) is added andcooked for 1 hour. 45.7 g TiCl₄ and 206.8 g toluene is added to activatethe solid to get the final catalyst.

1.5 ml of 25% triethyl aluminum is injected into the 3.4 liter reactorat 30° C. which is exclusive of air and moisture by nitrogen purge. 0.6ml 0.128 M cyclohexyl methyl dimethoxy silane and 10 mg catalyst inmineral oil is charged to reactor. Then 3.5 pound of hydrogen gas ischarged into the reactor. Then 1500 ml of liquid propylene is added intoreactor. The polymerization of propylene proceeds for 1 hour at 70° C.At the end of polymerization, the reactor is cooled down to 20° C. Thepolypropylene is completely dried in a vacuum oven. The results of thisand other examples are given in Table 1.

EXAMPLE 2

Example 1 is repeated but 172 g TiCl₄ is added instead of 50 g TiCl₄ at−20° C.

EXAMPLE 3

Example 1 is repeated but 130 g TiCl₄ is added instead of 50 g TiCl₄ at−20° C.

EXAMPLE 4

Example 2 is repeated but 60 ml of ethanol is added instead of 28 ml ofethanol, and the slurry of MgCl₂ solution in silica is washed withtoluene before TiCl₄ addition.

EXAMPLE 5

Example 4 is repeated but 12.5 g MgCl₂ is added instead of 10 g MgCl₂.

EXAMPLE 6

Example 3 is repeated but 10 ml DIBP is added instead of 5 ml DIBP.

EXAMPLE 7

Example 1 is repeated but Silica XPO-2410 available from Grace Davisonis added instead of SYLOPOL 2229.

EXAMPLE 8

Example 1 is repeated but Silica ES757 available from Ineos is addedinstead of SYLOPOL 2229.

EXAMPLE 9

Example 1 is repeated but Silica MD868 CM available from Ineos is addedinstead of SYLOPOL 2229.

TABLE 1 CE BD D50 XS MFI D50 Example kg/g cc/g μm wt % g/10 min μm <150vol % 1 3.8 — 49.99 — — — — 2 16.4 0.36 47.52 5.74 3.4 1284 0 3 17.70.37 46.6 4.78 5.6 1332 0 4 21 0.4 55.02 4.11 5.8 1466 0 5 17.8 0.3842.96 5.83 6.4 1335 0.3 6 20.7 0.388 48.51 3.8 3.6 1354 0.1 7 20.3 0.41427.72 3.75 5.4 880 0 8 20.3 0.455 28.75 3.41 4.1 501 0 9 17.5 0.37814.02 3.39 5 381 0.7

The characteristics of the catalysts and polymer products of Examples1–9 are summarized in Table 1. CE refers to catalytic efficiency, BDrefers to bulk density, the first D50 refers to an average diameter ofthe solid titanium catalyst component on a 50% by volume basis asdetermined by a Malvern Instrument, XS refers to xylene solubles, MFIrefers to melt flow index on a g/10 minute basis according to ASTMstandard D 1238, the second D50 refers to an average diameter of polymerproduct on a 50% by volume basis as determined by a Malvern Instrument,and <150 refers to the % by volume of polymer product having an averagediameter of less than 150 μm.

EXAMPLE 10

Example 4 is repeated without DIBP. The intermediate is activated using60 ml TiCl₄ and 60 ml hexane at 95° C. for 1 hour. The final catalysthas Ti 5.39% by weight and Mg 5.04% by weight.

Polymerization reactor is purified by 10 times pressurizing anddepressurizing with highly pure nitrogen. Vial with catalyst is placedin breaking device before the reactor tightening. TEA, ethylene,hydrogen (0.63 or 0.84 MPa), comonomer (4.4 g at 0.8 MPa) are fed intothe reactor in the mentioned order. The polymerization runs are startedat 80° C. Total pressure 2.1 MPa is maintained constant during 1-hourrun by continuous ethylene feeding. After 1 hour, the monomer is ventedoff and the polymer obtained is weighed. The catalyst activity isexpressed in g PE/g cat/hour. The results are given in Table 2.

TABLE 2 Cat amt. H₂ Activity mg MPa g PE/g cat/hour run 1 6.7 0.6310,298 run 2 8.7 0.84 7,586 5073 run 3 5.7 0.63 10,842

While the invention is explained in relation to certain embodiments, itis to be understood that various modifications thereof will becomeapparent to those skilled in the art upon reading the specification.Therefore, it is to be understood that the invention disclosed herein isintended to cover such modifications as fall within the scope of theappended claims.

1. A catalyst system for the polymerization of an olefin, comprising: asolid titanium catalyst component consisting essentially of an inorganictitanium compound, a magnesium-alcohol adduct, and a porous supporthaving at least one of a specific surface area of about 100 m²/g or moreand about 2,000 m²/g or less, a pore volume of about 0.2 cc/g or moreand about 5 cc/g or less, and a median particle size (by volume) ofabout 1 micron or more and about 200 microns or less; an organoaluminumcompound having at least one aluminum-carbon bond; and optionally anorganosilicon compound.
 2. The catalyst system of claim 1, wherein theporous support has at least two of a specific surface area of about 200m²/g or more and about 1,500 m²/g or less, a pore volume of about 0.3cc/g or more and about 4 cc/g or less, and a median particle size (byweight) of about 5 microns or more and about 150 microns or less.
 3. Thecatalyst system of claim 1, wherein the inorganic titanium compoundcomprises at least one selected from the group consisting of titaniumchloride, titanium bromide, titanium iodide, and titanium fluoride. 4.The catalyst system of claim 1, wherein the alcohol comprises at leastone selected from the group consisting of methanol, ethanol, n-propanol,isopropanol, n-butanol, iso-butanol, t-butanol, n-pentanol,iso-pentanol, hexanol, 2-ethylhexanol, decanol, cyclohexanol, andphenol.
 5. The catalyst system of claim 1, wherein the solid titaniumcatalyst component further comprises an internal electron donor.
 6. Thecatalyst system of claim 1, wherein the magnesium-alcohol adduct is madefrom an alcohol and an inorganic magnesium compound selected from thegroup consisting of magnesium chloride, magnesium bromide, magnesiumiodide, and magnesium fluoride.
 7. The catalyst system of claim 1,wherein the solid titanium catalyst component has a diameter from about25 microns to about 100 microns (on a 50% by volume basis).
 8. Thecatalyst system of claim 1, wherein the magnesium alcohol adduct is notdealcoholed.
 9. The catalyst system of claim 1, wherein the poroussupport has a specific surface area of about 300 m²/g or more and about1,000 m²/g or less, a pore volume of about 0.5 cc/g or more and about 3cc/g or less, and a median particle size (by volume) of about 10 micronsor more and about 100 microns or less.
 10. The catalyst system of claim1, wherein the porous support comprises at least one selected from thegroup consisting of silica, alumina, alumina-silicates, ceria, zeolites,clay, zirconia, titania, zinc oxide.
 11. The catalyst system of claim 1,wherein the alcohol comprises an alkyl alcohol containing from 1 toabout 12 carbon atoms.
 12. The catalyst system of claim 6, wherein themagnesium-alcohol adduct is made by contacting the alcohol and theinorganic magnesium at a molar ratio of the alcohol to the inorganicmagnesium compound of about 0.1:1 to about 1:0.1.
 13. The catalystsystem of claim 6, wherein the magnesium-alcohol adduct is made bycontacting the alcohol and the inorganic magnesium at a molar ratio ofthe alcohol to the inorganic magnesium compound of about 0.25:1 to about1:0.25.
 14. The catalyst system of claim 6, wherein themagnesium-alcohol adduct is made by contacting the alcohol and theinorganic magnesium at a molar ratio of the alcohol to the inorganicmagnesium compound of about 0.5:1 to about 1:0.5.
 15. The catalystsystem of claim 6, wherein the magnesium-alcohol adduct is made byheating the alcohol and the inorganic magnesium to a temperature fromabout 40° C. to about 200° C.
 16. The catalyst system of claim 6,wherein the magnesium-alcohol adduct is made by heating the alcohol andthe inorganic magnesium to a temperature from about 60° C. to about 140°C.
 17. The catalyst system of claim 6, wherein the magnesium-alcoholadduct is made by heating the alcohol and the inorganic magnesium to atemperature from about 80° C. to about 120° C.
 18. The catalyst systemof claim 6, wherein the magnesium-alcohol adduct is made by heating thealcohol and the inorganic magnesium for a time from about 5 minutes toabout 15 hours.
 19. The catalyst system of claim 6, wherein themagnesium-alcohol adduct is made by heating the alcohol and theinorganic magnesium for a period of time from about 30 minutes to about10 hours.
 20. The catalyst system of claim 6, wherein themagnesium-alcohol adduct is made by heating the alcohol and theinorganic magnesium for a period of time from about 1 hour to about 4hours.
 21. The catalyst system of claim 6, wherein the magnesium-alcoholadduct is made by heating the alcohol and the inorganic magnesium andthen recovering precipitation.
 22. A method of making a polyolefin,comprising: contacting an olefin with a catalyst system comprising asolid titanium catalyst component, the solid titanium catalyst componentconsisting essentially of an inorganic titanium compound, a magnesiumalcohol adduct made from an inorganic magnesium compound and an alcohol,and a porous support having at least one of a specific surface area ofabout 100 m²/g or more and about 2,000 m²/g or less, a pore volume ofabout 0.2 cc/g or more and about 5 cc/g or less, and a median particlesize (by volume) of about 1 micron or more and about 200 microns orless; a organoaluminum compound having at least one aluminum-carbonbond; and optionally an organosilicon compound to provide thepolyolefin.
 23. The method of claim 22, wherein the olefin comprises atleast one selected from the group consisting of ethylene, propylene,1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-hexene,3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, 1-tetradecene,1-eicosene, and vinylcyclohexane.
 24. The method of claim 22, whereinthe solid titanium catalyst component further comprises an internalelectron donor.